EP2862911A1 - Adhesive agent composition having improved bubble stability and method for preparing same - Google Patents
Adhesive agent composition having improved bubble stability and method for preparing same Download PDFInfo
- Publication number
- EP2862911A1 EP2862911A1 EP12879380.9A EP12879380A EP2862911A1 EP 2862911 A1 EP2862911 A1 EP 2862911A1 EP 12879380 A EP12879380 A EP 12879380A EP 2862911 A1 EP2862911 A1 EP 2862911A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- acrylate
- weight
- adhesive composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 137
- 239000000853 adhesive Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001070 adhesive effect Effects 0.000 claims abstract description 104
- 239000000178 monomer Substances 0.000 claims abstract description 88
- 239000011521 glass Substances 0.000 claims abstract description 72
- 239000000945 filler Substances 0.000 claims abstract description 65
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000000016 photochemical curing Methods 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 83
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 29
- -1 2-ethylhexyl Chemical group 0.000 claims description 23
- 238000001723 curing Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 18
- 239000006260 foam Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000009172 bursting Effects 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- VTCTUPUJLWMILI-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone 2-hydroxy-1,2-diphenylethanone Chemical compound OC(C(=O)c1ccccc1)c1ccccc1.CCOC(C(=O)c1ccccc1)c1ccccc1 VTCTUPUJLWMILI-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- ZQPGRCHQXDHWIL-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylbutan-1-one Chemical compound C=1C=C(SC)C=CC=1C(=O)C(C)(CC)N1CCOCC1 ZQPGRCHQXDHWIL-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
Definitions
- the present invention relates to an adhesive composition exhibiting improved bubble stability and a method for preparing the same.
- an adhesive composition typically contains bubbles, a method for increasing viscosity is widely used to secure bubble stability.
- the adhesive composition includes a small amount of acrylic acid, the adhesive composition exhibits high bubble stability in winter in which air temperature is low, whereas the adhesive composition exhibits deteriorated bubble stability in summer in which air temperature is high.
- Japanese Patent Laid-open Publication No. 2011-190290 discloses an adhesive composition including bubbles of carbon dioxide, inert gas such as argon, and the like.
- this publication is aimed at facilitating winding of an adhesive tape including the adhesive composition while suppressing protrusion of the adhesive composition, and does not disclose subject matter relating to stability of bubbles included in the adhesive composition, and the like.
- an adhesive composition includes: a copolymer in which 5 parts by weight to 50 parts by weight of a polar functional group-containing monomer is polymerized based on 100 parts by weight of a (meth)acrylic acid ester monomer; and hollow glass fillers or bubbles.
- the (meth)acrylic acid ester monomer may include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and combinations thereof.
- the polar functional group-containing monomer may include at least one selected from the group consisting of hydroxyl group-containing monomers, carboxyl group-containing monomers, nitrogen-containing monomers, and combinations thereof.
- the hollow glass fillers or the bubbles may have a spherical shape.
- the hollow glass fillers or the bubbles may have a diameter from about 20 ⁇ m to about 300 ⁇ m.
- the hollow glass fillers may be present in an amount of about 0.1 parts by weight to about 20 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester monomer.
- the bubbles may be present in an amount of about 0.1% by volume (vol%) to about 10 vol% by volume.
- the adhesive composition may have a density from about 0.4 g/m 3 to about 0.8 g/m 3 .
- a method for preparing an adhesive composition includes: preparing a copolymer by polymerizing about 5 parts by weight to about 50 parts by weight of a polar functional group-containing monomer based on 100 parts by weight of a (meth)acrylic acid ester monomer; preparing a mixture by adding a surfactant, a photoinitiator and a photocuring agent to the copolymer; and adding hollow glass fillers to the mixture or injecting bubbles into the mixture.
- the method may further include curing the mixture including the hollow glass filler or the bubbles therein.
- the adhesive composition prevents the hollow glass fillers or the bubbles in the copolymer from floating to a surface of the adhesive composition and then bursting, and exhibits improved bubble stability.
- the adhesive composition is coated onto one surface or both surfaces of acrylic foam, thereby allowing the adhesive composition-coated foam to be used as a foam tape.
- Fig. 1 shows SEM images of specimens of Example 1 and Comparative Example 1, respectively.
- an adhesive composition includes: a copolymer in which 5 parts by weight to 50 parts by weight of a polar functional group-containing monomer is polymerized based on 100 parts by weight of a (meth)acrylic acid ester monomer; and hollow glass fillers or bubbles.
- the (meth)acrylic acid ester monomer may be any (meth)acrylic acid ester monomer without limitation.
- the (meth)acrylic acid ester monomer may be an alkyl (meth)acrylate.
- an alkyl group included in the monomer has an excessively long chain, the adhesive composition can suffer from deterioration of cohesion and has difficulty in adjustment of glass transition temperature (Tg) and adhesion thereof.
- the (meth)acrylic acid ester monomer may be a C 1 to C 14 alkyl group-containing (meth)acrylic acid ester monomer.
- the acrylic acid ester monomer may include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and combinations thereof.
- the adhesive composition may include the polar functional group.
- the adhesive composition may be a copolymer of a monomer mixture of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer.
- the polar functional group-containing monomer includes the polar functional group copolymerizable with the (meth)acrylic acid ester monomer, and serves to adjust durability and cohesion of the adhesive composition.
- Examples of the polar functional group-containing monomer may include hydroxyl group-containing monomers, carboxyl group-containing monomers, and nitrogen-containing monomers.
- the polar functional group-containing monomer may be a hydroxyl group-containing monomer, without being limited thereto.
- the hydroxyl group-containing monomers may include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, and 2-hydroxypropylene glycol (meth)acrylate;
- examples of the carboxyl group-containing monomers may include (meth)acrylic acid, 2-(meth)acryloyloxy acetic acid, 3-(meth)acryloyloxy propylic acid, 4-(meth)acryloyloxy butyric acid, acrylic acid dimer, itaconic acid, maleic acid, and maleic anhydride;
- the nitrogen-containing monomers may include (meth) acrylamide, N-vinylpyrrolidone,
- the adhesive composition includes the hollow glass fillers or the bubbles.
- the amount of each of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer is limited, whereby the adhesive composition can stably include the hollow glass fillers or the bubbles while the hollow glass fillers or the bubbles maintain a certain shape.
- the hollow glass fillers or the bubbles due to interaction between functional groups of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer, which are present in a certain amount, the hollow glass fillers or the bubbles, which are forcibly added or injected into the adhesive composition according to the present invention or naturally generated therein, can be prevented from floating to the surface of the adhesive composition and then bursting. As such, since stability of the hollow glass fillers or the bubbles is maintained, the adhesive composition can maintain a certain level or higher of density and distribution of the hollow glass fillers or the bubbles regardless of external temperature.
- the adhesive composition may include about 5 parts by weight to about 50 parts by weight of the polar functional group-containing monomer based on 100 parts by weight of the (meth)acrylic acid ester monomer. Since the polar functional group-containing monomer is present in this amount, cohesion between the polar functional groups can cause interaction between the functional groups of both monomers and a finally cured adhesive composition can exhibit high cohesion and improved adhesion. Furthermore, the adhesive composition can have improved bubble stability by reducing a phenomenon that the forcibly injected bubbles float to the surface of the adhesive composition and then burst.
- the adhesive composition may include, for example, about 5 parts by weight to about 25 parts by weight of the carboxyl group-containing monomer.
- the adhesive composition may include, for example, about 15 parts by weight to about 40 parts by weight of the hydroxyl group-containing monomer.
- the adhesive composition can stably include the hollow glass fillers or the bubbles, which have a certain shape.
- the hollow glass fillers may include organic hollow glass fillers, inorganic hollow glass fillers, and combinations thereof.
- the hollow glass fillers may include hollow glass bubbles, hollow polymer microspheres, and the like.
- the glass bubbles refer to lightweight fillers exhibiting high strength and extremely excellent heat resistance and chemical resistance as hollow glass microspheres, which are composed of true glass and have a spherical shape and a low specific gravity. Since the glass bubbles have a much lower specific gravity than fillers used in existing plastics, it can be anticipated that the glass bubbles provide light weight due to the specific gravity thereof, reduction in use of resins, improvement in terms of dimensional stability, deformation after molding, processability, moldability, thermal insulation properties, water resistance, and the like.
- the hollow polymer microspheres also have a low specific gravity and may be included to reduce the weight of the adhesive composition.
- commercially available products of the hollow polymer microspheres may include Expancel, Micropearl, and the like.
- the adhesive composition according to the present invention includes the hollow glass fillers and thus can have a reduced specific gravity, the adhesive composition can be variously utilized while reducing an overall weight of an adherend to which the adhesive composition is applied.
- the bubbles may be formed of a gas.
- the gas may include various gases, such as nitrogen, carbon dioxide, inert gases including argon, and the like, without being limited thereto. It is important to use a gas that does not inhibit polymerization of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer nor mixing of additives therewith, as the gas forming the bubbles. Specifically, nitrogen is suitable among gases forming the bubbles since nitrogen does not inhibit polymerization or mixing and can reduce preparation costs.
- the hollow glass fillers or the bubbles typically have a spherical shape
- the hollow glass fillers or the bubbles may have a distorted spherical shape.
- the hollow glass fillers are similar to a tennis ball and can be kept in a spherical shape more easily than the bubbles.
- the hollow glass fillers or the bubbles may have a diameter from about 20 ⁇ m to about 300 ⁇ m, more specifically from about 50 ⁇ m to about 200 ⁇ m.
- the adhesive composition can secure light weight and cushioning properties, and stability of the adhesive composition can be checked by the diameter.
- the hollow glass fillers or the bubbles may be present in an independent form of each other or in a continuous form. That is, the adhesive composition may also include the hollow glass fillers or the bubbles in a continuous form, in which there is fusion-bonding between the hollow glass fillers, between the bubbles, or between the hollow glass fillers and the bubbles.
- the hollow glass fillers may be present in an amount of about 0.1 parts by weight to about 20 parts by weight, specifically about 3 parts by weight to about 10 parts by weight, based on 100 parts by weight of the (meth)acrylic acid ester monomer.
- the adhesive composition allows easy curing shrinkage and can maintain strength.
- the hollow glass fillers are present in an excessively small amount, it is difficult to obtain a desired density of the hollow glass fillers, and if the hollow glass fillers are present in an excessively large amount, the adhesive composition can have excessively increased viscosity and thus is difficult to stir or suffers from deterioration in adhesion.
- the hollow glass fillers or the bubbles may be uniformly dispersed in the adhesive composition. As the hollow glass fillers or the bubbles exhibit higher stability, the hollow glass fillers or the bubbles can be more uniformly dispersed in the adhesive composition and be contained in a larger amount in the adhesive composition. On the contrary, when the hollow glass fillers or the bubbles exhibit low stability, since the hollow glass fillers or the bubbles burst and thus exhibit deteriorated dispersibility and distribution, the hollow glass fillers or the bubbles cannot be uniformly dispersed and are contained in a relatively small amount in the adhesive composition.
- the hollow glass fillers or the bubbles may be present in an amount of about 0.1 vol% to about 10 vol%.
- the adhesive composition can exhibit flexibility and cushioning properties, thereby providing provide an increased attachment area.
- the bubbles can be uniformly present in the adhesive composition without bursting.
- the adhesive composition may have a density from about 0.4 g/m 3 to about 0.8 g/m 3 , specifically from about 0.5 g/m 3 to about 0.8 g/m 3 , more specifically from about 0.6 g/m 3 to about 0.8 g/m 3 . If the density of the adhesive composition is low, it can be inferred that the hollow glass fillers or the bubbles are uniformly dispersed well. On the other hand, if the density of the adhesive composition is high, it can be inferred that the hollow glass fillers or the bubbles have low dispersibility due to bursting thereof.
- the adhesive composition is coated onto one surface or both surfaces of acrylic foam, whereby the adhesive composition-coated foam can be used as a foam tape.
- An adhesive composition coating layer may have a thickness of, for example, about 100 ⁇ m to about 3000 ⁇ m, specifically from about 400 ⁇ m to about 2000 ⁇ m, without being limited thereto. Within this range, the adhesive composition can secure desired cushioning properties and can exhibit improved adhesion to curved or uneven surfaces.
- a method for preparing an adhesive composition includes: preparing a copolymer by polymerizing about 5 parts by weight to about 50 parts by weight of a polar functional group-containing monomer based on 100 parts by weight of a (meth)acrylic acid ester monomer; preparing a mixture by adding a surfactant, a photoinitiator and a photocuring agent to the copolymer; and adding hollow glass fillers to the mixture or injecting bubbles into the mixture.
- the method for preparing an adhesive composition includes preparing the copolymer by polymerizing about 5 parts by weight to about 50 parts by weight of the polar functional group-containing monomer based on 100 parts by weight of the (meth)acrylic acid ester monomer. Specifically, the preparation of the copolymer is achieved by thermal polymerization of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer. Here, thermal polymerization may be performed by any method known in the art.
- thermal polymerization may be performed at a temperature from about 50°C to about 70°C, specifically from about 50°C to about 60°C, for about 1 hour to about 3 hours, specifically for about 2 hours.
- the (meth)acrylic acid ester monomer and the polar functional group-containing monomer, which are subjected to polymerization may be added in a lump, separately or continuously added.
- the method for preparing an adhesive composition includes preparing the mixture by adding the surfactant, the photoinitiator and the photocuring agent to the copolymer in which the (meth)acrylic acid ester monomer and the polar functional group-containing monomer are polymerized.
- the surfactant, the photoinitiator and the photocuring agent, which are used are not particularly limited, and suitable additives may be used depending upon purposes of the adhesive composition.
- the surfactant may include ionic surfactants, silicone surfactants, and the like.
- the surfactant may be present in an amount of about 0.01 parts by weight to about 5 parts by weight, specifically about 0.05 parts by weight to about 3 parts by weight, based on 100 parts by weight of the polymerized resin.
- the photoinitiator may include, for example, benzoin, benzoin methyl ether, benzoin benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-ethyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone,
- the photoinitiator may be present in an amount of about 0.01 parts by weight to about 5 parts by weight, specifically about 0.05 parts by weight to about 3 parts by weight, based on 100 parts by weight of the polymerized resin.
- the photocuring agent can serve to adjust adhesion of the adhesive composition or to impart a crosslinked structure thereto depending upon the amount of the used photoinitiator.
- the photocuring agent may include polar monomers of polyfunctional acrylates and the like.
- the photocuring agent may include at least one selected from the group consisting of 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentanyl di(
- the photocuring agent may be present in an amount of about 0.05 parts by weight to about 2 parts by weight, based on 100 parts by weight of the polymerized resin. Within this range, there is no concern of deterioration in durability of the adhesive composition due to deterioration in cohesion, and there is also no concern of deterioration in durability thereof under high temperature and high humidity conditions.
- the method for preparing an adhesive composition includes adding the hollow glass fillers to the mixture or injecting the bubbles into the mixture.
- the hollow glass fillers may be added to the mixture, followed by stirring, thereby preparing an adhesive mixture.
- the adhesive mixture may be subjected to vacuum degassing using a vacuum pump, followed by injecting the bubbles into the adhesive mixture, thereby preparing an adhesive composition according to the present invention.
- the method for preparing an adhesive composition may further include curing the mixture including the hollow glass filler or the bubbles therein. By curing, the adhesive composition can be coated onto one surface or both surfaces of acrylic foam.
- the photoinitiator is required to be activated to cure the mixture, it is important to irradiate the mixture including the hollow glass filler or the bubbles therein with active energy rays.
- the active energy rays may include ionizing radiation, such as ⁇ -rays, ⁇ -rays, gamma rays, neutron rays, electron beams and the like, ultraviolet rays, and the like.
- ultraviolet rays are suitable as the active energy rays.
- the photo initiator may be activated to cause curing of the mixture using any irradiation energy, irradiation time, irradiation method and the like for the active energy rays without limitation.
- addition of the hollow glass fillers or injection of the bubbles and curing may be successively performed.
- the mixture including the hollow glass filler or the bubbles therein may be coated onto a predetermined surface, followed by drying, curing or the like, as needed, thereby preparing an adhesive composition coating layer.
- the hollow glass fillers or the bubbles may be added to or injected into the mixture including the surfactant, the photoinitiator and the photocuring agent, followed by coating the mixture onto a predetermined surface, and then subjected to heating or active energy ray irradiation, thereby preparing the adhesive composition coating layer.
- the adhesive composition coating layer may include the hollow glass fillers or the bubbles, which are uniformly dispersed.
- An acrylic foam tape was prepared in the same manner as in Example 1 except that the coating temperature was set to 25°C.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 25 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 5 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 40 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 1 except that 50 parts by weight of the polar acrylic acid monomer was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 1 except that 3 parts by weight of the polar acrylic acid monomer was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 3 parts by weight of the polar acrylic acid monomer was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 60 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- the adhesive compositions of Examples 1 to 6 including the copolymer, in which the (meth)acrylic acid ester monomer and the polar functional group-containing monomer were mixed in a ratio within the range according to the present invention had a density of 0.8 g/m 3 or less, regardless of external temperature. Since the adhesive compositions of Examples 1 to 6 had a lower density than those of Comparative Examples 1 to 3, it could be inferred that the bubbles were dispersed well in the adhesive compositions of Examples 1 to 6. In addition, since the adhesive compositions of Examples 1 to 6 had 10 or more bubbles per unit area, it could be seen that the adhesive compositions of Examples 1 to 6 exhibited excellent bubble stability.
- the adhesive compositions of Comparative Examples 1 to 3 included the copolymer in which the (meth)acrylic acid ester monomer and the polar functional group-containing monomer were mixed in a different ratio from the ratio according to the present invention, the adhesive compositions of Comparative Examples 1 to 3 had higher density than those of Examples 1 to 6, and had the small number of bubbles, that is, 7 or fewer bubbles. As such, it could be seen that the adhesive compositions of Comparative Examples 1 to 3 exhibited deterioration in dispersibility of the bubbles due to bursting of the bubbles and this result was caused by the monomer composition in the copolymer of the adhesive composition.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Provided is an adhesive composition, comprising: a copolymer in which a monomer containing 5 to 50 parts by weight of a polar functional group with respect to 100 parts by weight of a (meta) acrylic acid ester-based monomer is polymerized; and a hollow glass filler or bubbles. Also provided is a method for preparing the adhesive composition, comprising the steps of: preparing the copolymer by polymerizing 5 to 50 parts by weight of the monomer containing the polar function group, with respect to 100 parts by weight of the (meta) acrylic acid ester-based monomer; preparing a mixture by adding a surfactant, a photoinitiator, and a photocuring agent to the copolymer; and adding to the mixture the hollow glass filler or the bubbles.
Description
- The present invention relates to an adhesive composition exhibiting improved bubble stability and a method for preparing the same.
- Typically, when an adhesive composition contains bubbles, a method for increasing viscosity is widely used to secure bubble stability. However, even though viscosity is adjusted, if the adhesive composition includes a small amount of acrylic acid, the adhesive composition exhibits high bubble stability in winter in which air temperature is low, whereas the adhesive composition exhibits deteriorated bubble stability in summer in which air temperature is high. Thus, it is difficult to produce an acrylic foam tape including a bubble-dispersed adhesive composition which is not affected by external temperature.
- Japanese Patent Laid-open Publication No.
2011-190290 - It is an aspect of the present invention to provide an adhesive composition exhibiting excellent bubble stability regardless of external temperature or viscosity thereof.
- It is another aspect of the present invention to provide a method for preparing the adhesive composition as set forth above.
- In accordance with one aspect of the present invention, an adhesive composition includes: a copolymer in which 5 parts by weight to 50 parts by weight of a polar functional group-containing monomer is polymerized based on 100 parts by weight of a (meth)acrylic acid ester monomer; and hollow glass fillers or bubbles.
- The (meth)acrylic acid ester monomer may include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and combinations thereof.
- The polar functional group-containing monomer may include at least one selected from the group consisting of hydroxyl group-containing monomers, carboxyl group-containing monomers, nitrogen-containing monomers, and combinations thereof.
- The hollow glass fillers or the bubbles may have a spherical shape.
- The hollow glass fillers or the bubbles may have a diameter from about 20 µm to about 300 µm.
- The hollow glass fillers may be present in an amount of about 0.1 parts by weight to about 20 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester monomer.
- The bubbles may be present in an amount of about 0.1% by volume (vol%) to about 10 vol% by volume.
- The adhesive composition may have a density from about 0.4 g/m3 to about 0.8 g/m3.
- In accordance with another aspect of the present invention, a method for preparing an adhesive composition includes: preparing a copolymer by polymerizing about 5 parts by weight to about 50 parts by weight of a polar functional group-containing monomer based on 100 parts by weight of a (meth)acrylic acid ester monomer; preparing a mixture by adding a surfactant, a photoinitiator and a photocuring agent to the copolymer; and adding hollow glass fillers to the mixture or injecting bubbles into the mixture.
- The method may further include curing the mixture including the hollow glass filler or the bubbles therein.
- The adhesive composition prevents the hollow glass fillers or the bubbles in the copolymer from floating to a surface of the adhesive composition and then bursting, and exhibits improved bubble stability.
- In addition, the adhesive composition is coated onto one surface or both surfaces of acrylic foam, thereby allowing the adhesive composition-coated foam to be used as a foam tape.
-
Fig. 1 shows SEM images of specimens of Example 1 and Comparative Example 1, respectively. - Hereinafter, embodiments of the present invention will be described in detail. It should be understood that the following embodiments are provided for illustrative purposes only and are not to be construed in any way as limiting the present invention. The scope and sprit of the present invention should be defined only by the accompanying claims and equivalents thereof.
- In the drawings, portions irrelevant to the description are omitted for clarity. Like components will be denoted by like reference numerals throughout the specification.
- Hereinafter, embodiments of the present invention will be described in detail.
- In accordance with one aspect of the present invention, an adhesive composition includes: a copolymer in which 5 parts by weight to 50 parts by weight of a polar functional group-containing monomer is polymerized based on 100 parts by weight of a (meth)acrylic acid ester monomer; and hollow glass fillers or bubbles.
- The (meth)acrylic acid ester monomer may be any (meth)acrylic acid ester monomer without limitation. For example, the (meth)acrylic acid ester monomer may be an alkyl (meth)acrylate. Here, if an alkyl group included in the monomer has an excessively long chain, the adhesive composition can suffer from deterioration of cohesion and has difficulty in adjustment of glass transition temperature (Tg) and adhesion thereof. Thus, the (meth)acrylic acid ester monomer may be a C1 to C14 alkyl group-containing (meth)acrylic acid ester monomer.
- Specifically, the acrylic acid ester monomer may include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and combinations thereof.
- In formation of the adhesive composition, the adhesive composition may include the polar functional group. In this case, the adhesive composition may be a copolymer of a monomer mixture of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer.
- The polar functional group-containing monomer includes the polar functional group copolymerizable with the (meth)acrylic acid ester monomer, and serves to adjust durability and cohesion of the adhesive composition. Examples of the polar functional group-containing monomer may include hydroxyl group-containing monomers, carboxyl group-containing monomers, and nitrogen-containing monomers.
- In one embodiment, the polar functional group-containing monomer may be a hydroxyl group-containing monomer, without being limited thereto. Examples of the hydroxyl group-containing monomers may include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, and 2-hydroxypropylene glycol (meth)acrylate; examples of the carboxyl group-containing monomers may include (meth)acrylic acid, 2-(meth)acryloyloxy acetic acid, 3-(meth)acryloyloxy propylic acid, 4-(meth)acryloyloxy butyric acid, acrylic acid dimer, itaconic acid, maleic acid, and maleic anhydride; and examples of the nitrogen-containing monomers may include (meth) acrylamide, N-vinylpyrrolidone, and N-vinyl caprolactam, without being limited thereto.
- The adhesive composition includes the hollow glass fillers or the bubbles. Here, the amount of each of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer is limited, whereby the adhesive composition can stably include the hollow glass fillers or the bubbles while the hollow glass fillers or the bubbles maintain a certain shape.
- Specifically, due to interaction between functional groups of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer, which are present in a certain amount, the hollow glass fillers or the bubbles, which are forcibly added or injected into the adhesive composition according to the present invention or naturally generated therein, can be prevented from floating to the surface of the adhesive composition and then bursting. As such, since stability of the hollow glass fillers or the bubbles is maintained, the adhesive composition can maintain a certain level or higher of density and distribution of the hollow glass fillers or the bubbles regardless of external temperature.
- The adhesive composition may include about 5 parts by weight to about 50 parts by weight of the polar functional group-containing monomer based on 100 parts by weight of the (meth)acrylic acid ester monomer. Since the polar functional group-containing monomer is present in this amount, cohesion between the polar functional groups can cause interaction between the functional groups of both monomers and a finally cured adhesive composition can exhibit high cohesion and improved adhesion. Furthermore, the adhesive composition can have improved bubble stability by reducing a phenomenon that the forcibly injected bubbles float to the surface of the adhesive composition and then burst.
- When the polar functional group-containing monomer is a carboxyl group-containing monomer, the adhesive composition may include, for example, about 5 parts by weight to about 25 parts by weight of the carboxyl group-containing monomer. In addition, when the polar functional group-containing monomer is a hydroxyl group-containing monomer, the adhesive composition may include, for example, about 15 parts by weight to about 40 parts by weight of the hydroxyl group-containing monomer. Within this range, the adhesive composition can stably include the hollow glass fillers or the bubbles, which have a certain shape.
- The hollow glass fillers may include organic hollow glass fillers, inorganic hollow glass fillers, and combinations thereof. Specifically, the hollow glass fillers may include hollow glass bubbles, hollow polymer microspheres, and the like. The glass bubbles refer to lightweight fillers exhibiting high strength and extremely excellent heat resistance and chemical resistance as hollow glass microspheres, which are composed of true glass and have a spherical shape and a low specific gravity. Since the glass bubbles have a much lower specific gravity than fillers used in existing plastics, it can be anticipated that the glass bubbles provide light weight due to the specific gravity thereof, reduction in use of resins, improvement in terms of dimensional stability, deformation after molding, processability, moldability, thermal insulation properties, water resistance, and the like.
- The hollow polymer microspheres also have a low specific gravity and may be included to reduce the weight of the adhesive composition. For example, commercially available products of the hollow polymer microspheres may include Expancel, Micropearl, and the like.
- Therefore, since the adhesive composition according to the present invention includes the hollow glass fillers and thus can have a reduced specific gravity, the adhesive composition can be variously utilized while reducing an overall weight of an adherend to which the adhesive composition is applied.
- The bubbles may be formed of a gas. The gas may include various gases, such as nitrogen, carbon dioxide, inert gases including argon, and the like, without being limited thereto. It is important to use a gas that does not inhibit polymerization of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer nor mixing of additives therewith, as the gas forming the bubbles. Specifically, nitrogen is suitable among gases forming the bubbles since nitrogen does not inhibit polymerization or mixing and can reduce preparation costs.
- Although the hollow glass fillers or the bubbles typically have a spherical shape, the hollow glass fillers or the bubbles may have a distorted spherical shape. The hollow glass fillers are similar to a tennis ball and can be kept in a spherical shape more easily than the bubbles.
- Specifically, the hollow glass fillers or the bubbles may have a diameter from about 20 µm to about 300 µm, more specifically from about 50 µm to about 200 µm. Within this range of the diameter of the hollow glass fillers or the bubbles, the adhesive composition can secure light weight and cushioning properties, and stability of the adhesive composition can be checked by the diameter.
- In addition, the hollow glass fillers or the bubbles may be present in an independent form of each other or in a continuous form. That is, the adhesive composition may also include the hollow glass fillers or the bubbles in a continuous form, in which there is fusion-bonding between the hollow glass fillers, between the bubbles, or between the hollow glass fillers and the bubbles.
- The hollow glass fillers may be present in an amount of about 0.1 parts by weight to about 20 parts by weight, specifically about 3 parts by weight to about 10 parts by weight, based on 100 parts by weight of the (meth)acrylic acid ester monomer. Within this range, the adhesive composition allows easy curing shrinkage and can maintain strength. On the other hand, if the hollow glass fillers are present in an excessively small amount, it is difficult to obtain a desired density of the hollow glass fillers, and if the hollow glass fillers are present in an excessively large amount, the adhesive composition can have excessively increased viscosity and thus is difficult to stir or suffers from deterioration in adhesion.
- The hollow glass fillers or the bubbles may be uniformly dispersed in the adhesive composition. As the hollow glass fillers or the bubbles exhibit higher stability, the hollow glass fillers or the bubbles can be more uniformly dispersed in the adhesive composition and be contained in a larger amount in the adhesive composition. On the contrary, when the hollow glass fillers or the bubbles exhibit low stability, since the hollow glass fillers or the bubbles burst and thus exhibit deteriorated dispersibility and distribution, the hollow glass fillers or the bubbles cannot be uniformly dispersed and are contained in a relatively small amount in the adhesive composition.
- Specifically, the hollow glass fillers or the bubbles may be present in an amount of about 0.1 vol% to about 10 vol%. Within this range, the adhesive composition can exhibit flexibility and cushioning properties, thereby providing provide an increased attachment area. In addition, since the amount of the bubbles is maintained at a constant volume percentage, the bubbles can be uniformly present in the adhesive composition without bursting.
- The adhesive composition may have a density from about 0.4 g/m3 to about 0.8 g/m3, specifically from about 0.5 g/m3 to about 0.8 g/m3, more specifically from about 0.6 g/m3 to about 0.8 g/m3. If the density of the adhesive composition is low, it can be inferred that the hollow glass fillers or the bubbles are uniformly dispersed well. On the other hand, if the density of the adhesive composition is high, it can be inferred that the hollow glass fillers or the bubbles have low dispersibility due to bursting thereof.
- Therefore, since the amount of each of the monomers forming the copolymer in the adhesive composition is limited, the hollow glass fillers or the bubbles can be uniformly distributed, and the density of the adhesive composition can be maintained within the above range. In addition, the adhesive composition is coated onto one surface or both surfaces of acrylic foam, whereby the adhesive composition-coated foam can be used as a foam tape.
- An adhesive composition coating layer may have a thickness of, for example, about 100 µm to about 3000 µm, specifically from about 400 µm to about 2000 µm, without being limited thereto. Within this range, the adhesive composition can secure desired cushioning properties and can exhibit improved adhesion to curved or uneven surfaces.
- In accordance with another aspect of the present invention, a method for preparing an adhesive composition includes: preparing a copolymer by polymerizing about 5 parts by weight to about 50 parts by weight of a polar functional group-containing monomer based on 100 parts by weight of a (meth)acrylic acid ester monomer; preparing a mixture by adding a surfactant, a photoinitiator and a photocuring agent to the copolymer; and adding hollow glass fillers to the mixture or injecting bubbles into the mixture.
- The method for preparing an adhesive composition includes preparing the copolymer by polymerizing about 5 parts by weight to about 50 parts by weight of the polar functional group-containing monomer based on 100 parts by weight of the (meth)acrylic acid ester monomer. Specifically, the preparation of the copolymer is achieved by thermal polymerization of the (meth)acrylic acid ester monomer and the polar functional group-containing monomer. Here, thermal polymerization may be performed by any method known in the art.
- For example, thermal polymerization may be performed at a temperature from about 50°C to about 70°C, specifically from about 50°C to about 60°C, for about 1 hour to about 3 hours, specifically for about 2 hours. Here, the (meth)acrylic acid ester monomer and the polar functional group-containing monomer, which are subjected to polymerization, may be added in a lump, separately or continuously added.
- The method for preparing an adhesive composition includes preparing the mixture by adding the surfactant, the photoinitiator and the photocuring agent to the copolymer in which the (meth)acrylic acid ester monomer and the polar functional group-containing monomer are polymerized. Here, the surfactant, the photoinitiator and the photocuring agent, which are used, are not particularly limited, and suitable additives may be used depending upon purposes of the adhesive composition.
- The surfactant may include ionic surfactants, silicone surfactants, and the like. The surfactant may be present in an amount of about 0.01 parts by weight to about 5 parts by weight, specifically about 0.05 parts by weight to about 3 parts by weight, based on 100 parts by weight of the polymerized resin.
- The photoinitiator may include, for example, benzoin, benzoin methyl ether, benzoin benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-ethyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, α,α-methoxy-α-hydroxyacetophenone, 2-benzoyl-2-(dimethylamino)-1-[4-(4-morphonyl)phenyl]-1-butanone, 2,2-dimethoxy-2-phenylacetophenone, and the like, without being limited thereto.
- The photoinitiator may be present in an amount of about 0.01 parts by weight to about 5 parts by weight, specifically about 0.05 parts by weight to about 3 parts by weight, based on 100 parts by weight of the polymerized resin.
- The photocuring agent can serve to adjust adhesion of the adhesive composition or to impart a crosslinked structure thereto depending upon the amount of the used photoinitiator. For example, the photocuring agent may include polar monomers of polyfunctional acrylates and the like. Specifically, the photocuring agent may include at least one selected from the group consisting of 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentanyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, di(meth)acryloxy ethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, ethylene oxide-modified hexahydrophthalic acid di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, neopentyl glycol-modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(meth)acryloxyethyl isocyanurate, diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and urethane (meth)acrylate which is a reaction product of an isocyanate monomer and trimethylolpropane tri(meth)acrylate.
- The photocuring agent may be present in an amount of about 0.05 parts by weight to about 2 parts by weight, based on 100 parts by weight of the polymerized resin. Within this range, there is no concern of deterioration in durability of the adhesive composition due to deterioration in cohesion, and there is also no concern of deterioration in durability thereof under high temperature and high humidity conditions.
- The method for preparing an adhesive composition includes adding the hollow glass fillers to the mixture or injecting the bubbles into the mixture.
- When the adhesive composition simultaneously include the hollow glass fillers and the bubbles, first, the hollow glass fillers may be added to the mixture, followed by stirring, thereby preparing an adhesive mixture. Next, the adhesive mixture may be subjected to vacuum degassing using a vacuum pump, followed by injecting the bubbles into the adhesive mixture, thereby preparing an adhesive composition according to the present invention.
- The method for preparing an adhesive composition may further include curing the mixture including the hollow glass filler or the bubbles therein. By curing, the adhesive composition can be coated onto one surface or both surfaces of acrylic foam.
- Since the photoinitiator is required to be activated to cure the mixture, it is important to irradiate the mixture including the hollow glass filler or the bubbles therein with active energy rays. The active energy rays may include ionizing radiation, such as α-rays, β-rays, gamma rays, neutron rays, electron beams and the like, ultraviolet rays, and the like. In particular, ultraviolet rays are suitable as the active energy rays. In addition, the photo initiator may be activated to cause curing of the mixture using any irradiation energy, irradiation time, irradiation method and the like for the active energy rays without limitation.
- In addition, to suppress or prevent bursting of the hollow glass fillers or the bubbles, addition of the hollow glass fillers or injection of the bubbles and curing may be successively performed. Specifically, the mixture including the hollow glass filler or the bubbles therein may be coated onto a predetermined surface, followed by drying, curing or the like, as needed, thereby preparing an adhesive composition coating layer.
- That is, the hollow glass fillers or the bubbles may be added to or injected into the mixture including the surfactant, the photoinitiator and the photocuring agent, followed by coating the mixture onto a predetermined surface, and then subjected to heating or active energy ray irradiation, thereby preparing the adhesive composition coating layer. Here, the adhesive composition coating layer may include the hollow glass fillers or the bubbles, which are uniformly dispersed.
- Hereinafter, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be construed in any way as limiting the present invention.
- 11 parts by weight of a polar acrylic acid monomer was added to a 1 liter glass reactor based on 100 parts by weight of 2-ethylhexyl acrylate, followed by thermal polymerization, thereby obtaining a copolymer having a viscosity of 3500 cP. 0.5 parts by weight of Irgacure-651 (α,α-methoxy-α-hydroxyacetophenone) as a photoinitiator, and 0.35 parts by weight of 1,6-hexanediol diacrylate (HDDA) as a crosslinking agent were added to 100 parts by weight of the thermally polymerized resin, followed by sufficient stirring, thereby preparing a mixture.
- 4.5 parts by weight of glass bubbles and 1.5 parts by weight of silica were added to the prepared mixture, followed by sufficient stirring until the components were uniformly mixed. Next, the mixture was subjected to vacuum degassing using a vacuum pump.
- Next, nitrogen gas and 2 parts by weight of a silicone surfactant (based on 100 parts by weight of the thermally polymerized copolymer) were injected into the vacuum-degassed mixture using a foaming agent (Frother). Next, an adhesive composition was coated to a thickness of 0.8 mm onto a PET film through a UV curing apparatus, thereby manufacturing an acrylic foam tape. Here, a coating temperature was maintained at 10°C.
- An acrylic foam tape was prepared in the same manner as in Example 1 except that the coating temperature was set to 25°C.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 25 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 5 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 40 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 1 except that 50 parts by weight of the polar acrylic acid monomer was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 1 except that 3 parts by weight of the polar acrylic acid monomer was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 3 parts by weight of the polar acrylic acid monomer was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- An acrylic foam tape was prepared in the same manner as in Example 2 except that 60 parts by weight of 2-hydroxyethyl acrylate was present based on 100 parts by weight of 2-ethylhexyl acrylate.
- To evaluate stability of glass bubbles or bubbles according to different composition ratios of a (meth)acrylic acid ester monomer and a polar functional group-containing monomer, density and the number of bubbles were measured on each of specimens prepared in Examples and Comparative Examples.
1) Density: Density of each of the specimens of Examples and Comparative Examples was measured using an electronic solid gravimeter (DME-220E).
2) Number of bubbles: The number of bubbles was measured on an SEM image of each of the specimens of Examples and Comparative Examples, followed by analyzing the number of bubbles in a certain area (500 µm×1000 µm). Here, objects looking like protrusions were considered glass fillers, objects looking like dents were considered bubbles, and only the number of bubbles was determined.Table 1 Temperature (°C) Copolymer constitution (based on 100 parts by weight of 2-EHA) Density of adhesive composition (g/m3) Number of bubbles in adhesive composition Stability Example 1 10 AA 11 parts by weight 0.72 15 O Example 2 25 AA 11 parts by weight 0.74 12 O Example 3 25 2-HEA 25 parts by weight 0.73 14 O Example 4 25 2-HEA 5 parts by weight 0.69 16 O Example 5 25 2-HEA 50 parts by weight 0.72 13 O Example 6 10 AA 40 parts by weight 0.73 14 O Comparative Example 1 10 AA 3 parts by weight 0.81 7 X Comparative Example 2 25 AA 3 parts by weight 0.83 6 X Comparative Example 3 25 2-HEA 60 parts by weight 0.84 6 X - Referring to Table 1, the adhesive compositions of Examples 1 to 6 including the copolymer, in which the (meth)acrylic acid ester monomer and the polar functional group-containing monomer were mixed in a ratio within the range according to the present invention, had a density of 0.8 g/m3 or less, regardless of external temperature. Since the adhesive compositions of Examples 1 to 6 had a lower density than those of Comparative Examples 1 to 3, it could be inferred that the bubbles were dispersed well in the adhesive compositions of Examples 1 to 6. In addition, since the adhesive compositions of Examples 1 to 6 had 10 or more bubbles per unit area, it could be seen that the adhesive compositions of Examples 1 to 6 exhibited excellent bubble stability.
- On the contrary, since the adhesive compositions of Comparative Examples 1 to 3 included the copolymer in which the (meth)acrylic acid ester monomer and the polar functional group-containing monomer were mixed in a different ratio from the ratio according to the present invention, the adhesive compositions of Comparative Examples 1 to 3 had higher density than those of Examples 1 to 6, and had the small number of bubbles, that is, 7 or fewer bubbles. As such, it could be seen that the adhesive compositions of Comparative Examples 1 to 3 exhibited deterioration in dispersibility of the bubbles due to bursting of the bubbles and this result was caused by the monomer composition in the copolymer of the adhesive composition.
Claims (10)
- An adhesive composition comprising:a copolymer in which 5 parts by weight to 50 parts by weight of a polar functional group-containing monomer is polymerized based on 100 parts by weight of a (meth)acrylic acid ester monomer, andhollow glass fillers or bubbles.
- The adhesive composition according to claim 1, wherein the acrylic acid ester monomer comprises at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and combinations thereof.
- The adhesive composition according to claim 1, wherein the polar functional group-containing monomer comprises at least one selected from the group consisting of hydroxyl group-containing monomers, carboxyl group-containing monomers, nitrogen-containing monomers, and combinations thereof.
- The adhesive composition according to claim 1, wherein the hollow glass fillers or the bubbles have a spherical shape.
- The adhesive composition according to claim 1, wherein the hollow glass fillers or the bubbles have a diameter from 20 µm to 300 µm.
- The adhesive composition according to claim 1, wherein the hollow glass fillers are present in an amount of 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the (meth)acrylic acid ester monomer.
- The adhesive composition according to claim 1, wherein the bubbles are present in an amount of 0.1 vol% to 10 vol% per unit volume.
- The adhesive composition according to claim 1, wherein the adhesive composition has a density from 0.4 g/m3 to 0.8 g/m3.
- A method for preparing an adhesive composition, comprising:preparing a copolymer by polymerizing 5 parts by weight to 50 parts by weight of a polar functional group-containing monomer based on 100 parts by weight of a (meth)acrylic acid ester monomer;preparing a mixture by adding a surfactant, a photoinitiator and a photocuring agent to the copolymer; andadding hollow glass fillers to the mixture or injecting bubbles into the mixture.
- The method according to claim 9, further comprising:curing the mixture comprising the hollow glass filler or the bubbles therein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120065365A KR101534898B1 (en) | 2012-06-19 | 2012-06-19 | Adhesive composition with improved foam stability and the method for manufacturing the same |
| PCT/KR2012/010849 WO2013191339A1 (en) | 2012-06-19 | 2012-12-13 | Adhesive agent composition having improved bubble stability and method for preparing same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP2862911A1 true EP2862911A1 (en) | 2015-04-22 |
| EP2862911A4 EP2862911A4 (en) | 2015-08-05 |
| EP2862911B1 EP2862911B1 (en) | 2020-05-06 |
Family
ID=49768914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12879380.9A Active EP2862911B1 (en) | 2012-06-19 | 2012-12-13 | Adhesive agent composition having improved bubble stability and method for preparing same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20150133583A1 (en) |
| EP (1) | EP2862911B1 (en) |
| JP (1) | JP6238374B2 (en) |
| KR (1) | KR101534898B1 (en) |
| CN (1) | CN104364332A (en) |
| TW (1) | TWI475083B (en) |
| WO (1) | WO2013191339A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163884B (en) * | 2013-05-20 | 2016-12-28 | 3M创新有限公司 | Curable acrylic composition, acrylic adhesive tapes, acrylic compounds rubber roll and the method preparing this acrylic compounds rubber roll |
| KR101925922B1 (en) * | 2014-12-24 | 2018-12-06 | 주식회사 엘지화학 | Acrylic adhesive sheet, adhesive tape for medical treatment and method of producing the same |
| KR20180101536A (en) * | 2016-01-18 | 2018-09-12 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Pressure sensitive adhesive with filler |
| KR102404191B1 (en) | 2017-05-30 | 2022-05-30 | 도레이 카부시키가이샤 | Separator element |
| KR102018061B1 (en) | 2017-11-28 | 2019-09-04 | 주식회사 영우 | Pressure sensitive adhesive tape comprising an ultraviolet curable adhesive composition having a low hardening shrinkage |
| JP7025046B2 (en) | 2020-01-28 | 2022-02-24 | Ｎｅｃプラットフォームズ株式会社 | Test system, test method, and program |
| KR102379084B1 (en) | 2021-09-30 | 2022-03-24 | 윤미라 | (Ultraviolet curable resin composition and manufacturing method of UV curable laminate sheet comprising same |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388424A (en) * | 1981-11-05 | 1983-06-14 | Scm Corporation | Caulk containing microballoons |
| JPH11106721A (en) * | 1997-09-30 | 1999-04-20 | Sekisui Chem Co Ltd | Production of pressure-sensitive adhesive tape |
| JP5384774B2 (en) * | 2000-08-31 | 2014-01-08 | スリーエム イノベイティブ プロパティズ カンパニー | Acrylic foam adhesive and method for producing the same |
| JP2003041232A (en) * | 2001-07-30 | 2003-02-13 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive and pressure-sensitive adhesive tape |
| JP5408640B2 (en) * | 2006-09-04 | 2014-02-05 | 日東電工株式会社 | Ultraviolet curable adhesive composition, ultraviolet curable adhesive sheet and method for producing the same |
| US20100021730A1 (en) * | 2006-10-12 | 2010-01-28 | Nitto Denko Corporation | Acrylic pressure-sensitive adhesive tape or sheet, and method for producing the same |
| JP5089201B2 (en) * | 2007-03-12 | 2012-12-05 | 日東電工株式会社 | Acrylic adhesive tape or sheet and method for producing the same |
| EP2194105B1 (en) * | 2007-09-26 | 2013-05-08 | Denki Kagaku Kogyo Kabushiki Kaisha | Adhesive compositions and jointing method |
| JP5483835B2 (en) * | 2007-10-22 | 2014-05-07 | 日東電工株式会社 | Heat-foaming type removable acrylic adhesive tape or sheet |
| JP5570706B2 (en) * | 2008-05-29 | 2014-08-13 | 日東電工株式会社 | Acrylic pressure sensitive adhesive tape or sheet |
| KR101371909B1 (en) * | 2008-06-19 | 2014-03-10 | 주식회사 엘지화학 | Pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheet comprising the same |
| JP5563411B2 (en) * | 2009-10-16 | 2014-07-30 | リンテック株式会社 | Adhesive composition, adhesive and optical film |
| JP5568290B2 (en) * | 2009-11-30 | 2014-08-06 | 日東電工株式会社 | Adhesive tape |
| JP2011190290A (en) * | 2010-03-11 | 2011-09-29 | Nitto Denko Corp | Adhesive tape |
| JP2012117040A (en) * | 2010-11-12 | 2012-06-21 | Nitto Denko Corp | Pressure-sensitive adhesive tape or sheet |
| KR101400558B1 (en) * | 2011-12-07 | 2014-05-29 | (주)엘지하우시스 | Base material composition of foam tape, foam tape using the same and manufacturing method thereof |
| JP5950669B2 (en) * | 2012-04-16 | 2016-07-13 | 日東電工株式会社 | Adhesive sheet and adhesive composition |
-
2012
- 2012-06-19 KR KR1020120065365A patent/KR101534898B1/en active IP Right Grant
- 2012-12-13 JP JP2015518313A patent/JP6238374B2/en active Active
- 2012-12-13 EP EP12879380.9A patent/EP2862911B1/en active Active
- 2012-12-13 CN CN201280074017.0A patent/CN104364332A/en active Pending
- 2012-12-13 US US14/400,570 patent/US20150133583A1/en not_active Abandoned
- 2012-12-13 WO PCT/KR2012/010849 patent/WO2013191339A1/en active Application Filing
-
2013
- 2013-06-14 TW TW102121187A patent/TWI475083B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013191339A1 (en) | 2013-12-27 |
| CN104364332A (en) | 2015-02-18 |
| JP2015525282A (en) | 2015-09-03 |
| KR20130142284A (en) | 2013-12-30 |
| TWI475083B (en) | 2015-03-01 |
| EP2862911A4 (en) | 2015-08-05 |
| TW201400567A (en) | 2014-01-01 |
| JP6238374B2 (en) | 2017-11-29 |
| KR101534898B1 (en) | 2015-07-07 |
| EP2862911B1 (en) | 2020-05-06 |
| US20150133583A1 (en) | 2015-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2862911B1 (en) | Adhesive agent composition having improved bubble stability and method for preparing same | |
| EP2873705B1 (en) | Flame retardant adhesive agent composition having improved gas bubble stability, and method for preparing same | |
| EP2302012B1 (en) | Pressure-sensitive adhesive composition, polarization plate, and liquid crystal display | |
| KR101548784B1 (en) | Substrate film and manufacturing method thereof | |
| KR101565630B1 (en) | Solventless composition and manufacturing method thereof | |
| JP2009057550A (en) | Adhesive material | |
| JP2020037700A (en) | Impact absorption sheet | |
| KR102155180B1 (en) | Dual cure adhesive composition | |
| KR100678795B1 (en) | Pressure-sensitive adhesive compositions and adhesive films | |
| US20210332273A1 (en) | Porous adhesive film, optical member comprising same, and optical display device comprising same | |
| JP4503216B2 (en) | Optical hard coat film | |
| KR101687059B1 (en) | Pressure sensitive adhesive composition | |
| JP5903889B2 (en) | Hard coat film and front protective plate | |
| KR20120056175A (en) | Pressure-sensitive adhesive composition for touch panel, pressure-sensitive adhesive film and touch panel | |
| JP6379672B2 (en) | Transparent substrate | |
| JP2019164293A (en) | Image display device, copolymer solution, and film material | |
| JP2022553681A (en) | Curable composition | |
| KR20170105178A (en) | Double-sided adhesive tape and mehod of the same | |
| KR20140088431A (en) | Resin composition for release film comprising itaconic acid ester with long alkyl side chain | |
| KR101266219B1 (en) | Pressure-sensitive adhesive composition, polarizer and liquid crystal display | |
| JP2016107439A (en) | Transparent substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20141201 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| RA4 | Supplementary search report drawn up and despatched (corrected) |
Effective date: 20150706 |
|
| RIC1 | Information provided on ipc code assigned before grant |
Ipc: C09J 4/02 20060101AFI20150630BHEP Ipc: C09J 133/08 20060101ALI20150630BHEP Ipc: C09J 7/00 20060101ALI20150630BHEP Ipc: C08F 220/18 20060101ALI20150630BHEP Ipc: C09J 11/00 20060101ALI20150630BHEP |
|
| DAX | Request for extension of the european patent (deleted) | ||
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: LG CHEM, LTD. |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20180618 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20200103 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1266684 Country of ref document: AT Kind code of ref document: T Effective date: 20200515 Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602012070012 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200506 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200906 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200907 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200806 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200807 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200806 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1266684 Country of ref document: AT Kind code of ref document: T Effective date: 20200506 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602012070012 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20210209 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20201231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201213 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201213 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201231 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200506 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201231 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20231120 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20231121 Year of fee payment: 12 Ref country code: DE Payment date: 20231120 Year of fee payment: 12 |